US4544542A - Method for oxidation of flue gas desulfurization absorbent and the product produced thereby - Google Patents

Method for oxidation of flue gas desulfurization absorbent and the product produced thereby Download PDF

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US4544542A
US4544542A US06/600,710 US60071084A US4544542A US 4544542 A US4544542 A US 4544542A US 60071084 A US60071084 A US 60071084A US 4544542 A US4544542 A US 4544542A
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Prior art keywords
pellets
absorbent
calcium
constituents
binder
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US06/600,710
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English (en)
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Peter A. Angevine
Sune Bengtsson
George P. Koudijs
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Technip USA Corp
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Dorr Oliver Inc
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Priority to CA000473534A priority patent/CA1224010A/en
Priority to ZA85979A priority patent/ZA85979B/xx
Assigned to DORR-OLIVER INCORPORATED, A CORP OF DEL reassignment DORR-OLIVER INCORPORATED, A CORP OF DEL ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BENGTSSON, SUNE, KOUDIJS, GEORGE P., ANGEVINE, PETER A.
Priority to DE8585301918T priority patent/DE3586880T2/de
Priority to EP85301918A priority patent/EP0159807B1/en
Priority to ES541606A priority patent/ES8701518A1/es
Priority to AT0102685A priority patent/AT393801B/de
Priority to DK157985A priority patent/DK157985A/da
Priority to JP60081213A priority patent/JPS60232233A/ja
Priority to AU41293/85A priority patent/AU4129385A/en
Priority to CN198585104649A priority patent/CN85104649A/zh
Publication of US4544542A publication Critical patent/US4544542A/en
Application granted granted Critical
Priority to ES555055A priority patent/ES8707288A1/es
Assigned to BANCBOSTON FINANCIAL COMPANY, A CORP OF CT reassignment BANCBOSTON FINANCIAL COMPANY, A CORP OF CT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DORR VENTURES, INC., A DE CORP.
Assigned to CONTINENTAL ILLINOIS NATIONAL BANK AND TRUST COMPANY OF CHICAGO, 231 SOUTH LASALLE STREET, CHICAGO, ILLINOIS 60697 reassignment CONTINENTAL ILLINOIS NATIONAL BANK AND TRUST COMPANY OF CHICAGO, 231 SOUTH LASALLE STREET, CHICAGO, ILLINOIS 60697 MORTGAGE (SEE DOCUMENT FOR DETAILS). Assignors: DORR-OLIVER VENTURES INCORPORATED
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/508—Sulfur oxides by treating the gases with solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C01F11/464—Sulfates of Ca from gases containing sulfur oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • a typical dry FGD system comprises: (1) a pre-dust collector for removing fly ash, consisting of an electrostatic precipitator, cyclones or other dedusting equipment; (2) a sulfur scrubbing system, consisting of a liquor preparation system for preparing milk of lime slurry absorbent and a spray drying tower where the absorbent is injected into the flue gas to absorb sulfur dioxide (SO 2 ) and (3) a final dust collecting system.
  • a pre-dust collector for removing fly ash, consisting of an electrostatic precipitator, cyclones or other dedusting equipment
  • sulfur scrubbing system consisting of a liquor preparation system for preparing milk of lime slurry absorbent and a spray drying tower where the absorbent is injected into the flue gas to absorb sulfur dioxide (SO 2 )
  • SO 2 sulfur dioxide
  • the dry powder product contains both calcium sulfite and calcium sulfate and it has been suggested that this powder be reslurried and then subjected to oxidation by bubbling air therethrough to convert the calcium sulfite to calcium sulfate in accordance with the teachings of the "wet process" prior art as described above.
  • a characteristic of the dry FGD system is that the liquid phase of the fresh absorbent when injected into the spray-drying tower, is very nearly completely evaporated when the flue gas leaves the tower.
  • the dry, spent absorbent of fine-grained particles is first entrained in the desulfurized flue gas and is then partially separated and collected in the bottom section of the spray-drying tower, with the remaining entrained portion removed from the flue gas flow in a final dust-collecting system, usually a bag filter.
  • the system for preparing and injecting the liquid absorbent comprises:
  • One or more injection nozzles mounted on the spray drying tower for dispersing the absorbent liquor into the flue gas stream.
  • the recycle ratio is typically 3:1; i.e., three parts of recycled spent absorbent to one part of raw feed.
  • the calcuim sulfite is directly formed when milk of lime reacts with gaseous sulfur dioxide. In the temperature range of 70°-150° C., at which a spray-drying tower normally operates in FGD systems, and because of the relatively low oxygen levels of 3-5% in the flue gas, only a small part of the calcium sulfite is oxidized into the sulfate form.
  • the flue gas also contains an entrained fly-ash component which must be dealt with.
  • Fly-ash typically contains the following compounds:
  • West German Application DE No. 3015977 published Nov. 11, 1981, is directed to a flue gas desulfurization process and system for treating boiler off-gases in which spent absorbent containing a mixture of CaSO 3 and CaSO 4 is separated from the flue gas and injected into a region of the boiler combustion chamber in which an excess of air is present and the temperature therein is not substantially more than 800° C., and is preferably less than 800° C., to bring about oxidation of CaSO 3 to CaSO 4 .
  • European patent application No. 74,258 (A/S Niro Atomizer), published Mar. 16, 1983, is directed to a process for treating spent absorbents resulting from desulfurization of flue gas in a spray drying-absorption process, the absorbents containing substantial amounts of sulfite.
  • the sulfite is oxidized into sulfate by heating the spent absorbent in the presence of an oxygen-containing gas at temperatures in the range of 350°-600° C.
  • West German patent application DE No. 3135200 (L and C Steinmuller GmbH), published Mar. 17, 1983, is directed to a process for the treatment of the end products of flue gas desulfurization, the flue gas desulfurization being effect by absorption of sulfur oxides in a spray drier with a calcium-containing suspension or in a reactor with dry granular calcium-containing absorbent.
  • the end products of the flue gas desulfurization comprise the compounds, calcium sulfite hemihydrate and/or calcium sulfite and/or calcium sulfate dihydrate and/or calcium sulfate hemihydrate and/or calcium sulfate, with the balance the unreacted absorbent Ca(OH) 2 .
  • the calcium sulfite-containing end products are treated by dry oxidation with air at temperatures between 400° and 800° C. and, preferably, between 400° and 600° C.
  • the process of this invention calls for oxidizing a powder-like calcium sulfite material, which is the waste product or spent absorbent of a flue gas desulfurization process, to produce a pelletized calcium sulfate anhydrite product having commercial utility.
  • the term "calcium sulfite material” means the FGD product as received from the spray drying tower of a dry flue gas desulfurization process. It is the reaction product of a milk of lime slurry and sulfur dioxide at a temperature in the range 100°-180° C. and contains calcium sulfite, calcium sulfate and small amounts of other calcium-sulfur compounds, binders and inerts.
  • the powder-like, fine-grained calcium sulfite material containing a small amount (say, 1 to 3% by weight) of relatively low-melting constituents is subjected to oxidation in a fluidized bed reactor in which air is the fluidizing medium and the operating temperature of the reactor is maintained in the range from 700° to 1000° C. and, preferably, at a temperature over 800° C.
  • the relatively low-melting or binder constituent of the calcium sulfite material is in the liquid phase and this small amount of sticky molten compounds produces pelletization of the fine-grained spent absorbent.
  • the process achieves a high oxidation yield of calcium sulfite, and, in addition to the oxidation of calcium sulfite, any calcium sulfide formed by disproportionation (as described hereinafter) is also oxidized to calcium sulfate.
  • a controlled pelletization is essential: addition of small amounts of low-melting constituents are made to calcium sulfite material deficient in such constituents to assure adequate pelletization.
  • the addition of compounds which react with the binder compounds at the operating temperature of the reactor to form high melting compounds is undertaken to reduce the molten portion of the fluidized calcium sulfite material so that excessive pelletization (lump formation) is avoided.
  • Another method for reducing the binder content of the calcium sulfite material is to employ countercurrent washing of the calcium sulfite material to dissolve out the excess binder present before the oxidation treatment.
  • high-melting or low-melting compounds When high-melting or low-melting compounds are to be provided for reaction in the oxidation process, they can be added, as described above, directly to the calcium-sulfite material feed, or such compounds may be added to the fresh absorbent liquor before it enters the spray drying tower used in the flue gas desulfurization process.
  • a portion of the pellets produced in the process may be ground to a particle size intermediate that of the spent absorbent raw material and the oxidized pellet product and then fed (recycled) into the fluidized bed reactor with the calcium sulfite feed as nuclei for pelletization.
  • FIG. 1 is a flow chart and block diagram of an FGD system with the added feature of an oxidation system in accordance with the present invention
  • FIG. 2 is a graph comprising a series of curves recording the residual calcium sulfite content of an FGD product undergoing oxidation for a two hour period plotted against temperature at various excess oxygen contents and
  • FIG. 3 is a graph comprising a series of curves recording the calcium sulfide content of an FGD product subjected to oxidation for a two hour period plotted against temperature at various excess oxygen contents.
  • the sulfate content must be the predominant constituent and the amount of other constituents should not fluctuate too widely. These two conditions mean that the fly-ash content must lie in the range between 0 and 10% of the total weight of dry FGD product. Consequently, this requirement means that a pre-dust collector with a collecting efficiency of 80-90% of the total fly-ash in the boiler flue gas, should be installed upstream of the spray-drying tower.
  • fly-ash content of the dry FGD product could vary between 25 and 200% of the total calcium compounds, which is unacceptable for commercial use in most cement mills.
  • boilers operate at flame temperatures above 1200°-1400° C., at which the silica as well as iron and aluminum oxides combine to form a complex compound, similar to the process which takes place in clinker kiln in a cement mill. This means that the compounds in the fly-ash are not available individually but are fixed in the Fe-Al-Si complex compounds.
  • the pelletized product is free flowing and dust free and therefore convenient to handle, store and transport.
  • pellets will stay in the bed, which is essential to complete oxidation to a high degree.
  • the basic mechanism for this pelletization is to have a relatively small portion (1-3%) of the fluidized-bed material molten at the operating temperature range.
  • This liquid phase has usually sticky characteristics and therefore can serve as a binding agent for binding the particles together.
  • the liquid portion of the fluidized bed may consist of pure compounds, having a melting point below the operating temperature; however, it is well known that the melting point of specific mixtures (eutectics) of certain pure compounds can be considerably lower than the melting point of each individual pure component.
  • Satisfactory pelletization is defined as capture of 85 to 95% of the feed material.
  • Pelletization was immediately apparent in the initial test work done and was found to be a function of chloride content and operating temperature. Good pellet growth was achieved at 600° C. with 4% Cl, 700° C. with 2.6% Cl and 800° C. with 2% Cl.
  • Impurities and/or inerts in the feed material do not tend to pelletize and are preferentially separated from the product and carried out with the stack gases. This means that large quantities of inerts results in high carryover. The feature of this phenomena is that it improves the purity of the bed product.
  • the dry FGD product normally contains a varying amount of calcium chloride, dependent on the sulfur/chlorine ratio of the particular coal used.
  • Suitable binders are sodium and potassium compounds like Na 2 CO 3 , NaOH (which forms Na 2 CO 3 in the presence of CO 2 ), K 2 SO 4 and K 2 CO 3 .
  • Other binding agents worthy of consideration are Na 2 SiO 3 and (NH 4 ) 2 SO 4 .
  • NaCl or KCl can also certainly serve as binders when added to the feed, the chloride content of the pelletized product should be kept low when used in cement, and therefore addition of these chlorides are normally not desired.
  • the activity of a portion of the binding agents can also be neutralized by adding a suitable component to the FGD product which reacts with certain binding agents in such a way that compounds with a higher melting point are formed with the chloride being driven off as a vapor.
  • a suitable component to the FGD product which reacts with certain binding agents in such a way that compounds with a higher melting point are formed with the chloride being driven off as a vapor.
  • silica which reacts with CaCl 2 in the presence of water according to
  • Calcium silicate has a substantially higher melting point then calcium chloride.
  • FIG. 3 shows that CaS is formed only when the material is heated well above 500° C. and increases initially with increasing temperature.
  • the maximum sulfide content is formed at around 575° C. When heated above 575° C., the CaS content decreases steadily as temperature increases.
  • the same graph shows that the CaS content is lower when oxygen available for reaction is increased; however, it is not commercially attractive to provide more than about 5% excess oxygen.
  • CaS is an undesired compound in the FGD product. When applied as technical anhydrite in the building industry, it evolves a nuisance odor due to the generation of H 2 S when in contact with water; therefore, it is important to minimize the CaS content of the final product.
  • FIG. 2 shows that the residual CaSO 3 content after heating decreases continuously with increasing temperature.
  • the FGD product has to be oxidized at a temperature well above 700° C. to achieve a high oxidation rate (over 95%) and low residual sulfite and sulfide content.
  • the oxidation temperature is preferably over 800° C. to produce product pellets which are oxidized at least 95%.
  • the oxidizing system of the invention is shown as applied to treat the FGD product of a system for handling the flue-gas from a coal-burning boiler.
  • the flue-gas generated in boiler 10 passes through conduit 11 to the electrostatic precipitator 15 wherein the fly-ash entrained in the flue-gas in precipitated and removed from the system through outlets 16.
  • the electrostatic precipitator is effective to remove 90-95% of the fly-ash from the flue gas.
  • the relatively dust-free flue-gas passes from the electrostatic precipitator 15 to the spray drying tower 20 through conduit 17.
  • a slurry of milk of lime, Ca(OH) 2 is sprayed through the flue-gas from one or more injection nozzles 23.
  • a reaction occurs at the tower temperature of 100°-180° C. between the milk of lime slurry and the sulfur dioxide, SO 2 , to form calcium sulfite material (as defined above).
  • a large part of the calcium sulfite material falls to the bottom of spray drying tower 20 and is removed from the spray drying tower through conduit 21.
  • the gas passes from spray drying tower 20 to bag house 25 through conduit 22.
  • the gas is separated from any calcium sulfite material entrained therein and then leaves the bag house through conduit 27 for possible further treatment (not shown) and ultimate discharge through stack 28.
  • the calcium sulfite material (52 ⁇ to 100 ⁇ average diameter) separated in the bag house 25 leaves that unit through conduit 26.
  • the conduits 21 and 26 discharge their portions of the FGD product flow into line 29 which joins lines 51 and 43.
  • the flow from line 29 is split (by means not shown) so that a portion of the flow passes into line 51 and the remainder into line 43.
  • Line 51 is connected to the fluidized bed reactor 55 and the FGD product introduced thereby forms the bed material thereof.
  • Line 57 introduces a flow of air into the bottom of reactor 55 as the fluidizing medium for the bed which is supported on the constriction plate 54 of reactor 55.
  • Fuel preferably oil or gas, is introduced through line 62 in an amount sufficient to maintain a temperature in the range from about 700° C. to about 1000° C., preferably above 800° C. In this temperature range, in the presence of the air introduced as the fluidizing medium, the FGD product (calcium sulfite material) is oxidized to calcium sulfate.
  • nuclei of a size between that of the fine grained feed and the desired pellets are provided by a grinder 60.
  • Grinder 60 receives pellets formed in the fluidized bed reactor 55 through line 59 and reduces them to the desired size. These nuclei are then returned to the fluidized bed reactor 55 through line 61.
  • appropriate additives may be introduced into the feed FGD material through line 53 (in dotted line showing).
  • Na 2 CO 3 is added where insufficient binder is present in the feed
  • silica is added where excessive binder is present to form high melting compounds with some portion of the binder compounds.
  • the oxidized product pellets (0.5 mm to 5 mm average diameter), composed primarily of calcium sulfate, are withdrawn from the fluidized bed reactor 55 through outlet conduit 52 to a cooler unit 66 to cool the oxidized product pellets to ambient temperature.
  • That portion of the FGD product which passes from line 29 to line 43 is conducted to the repulper 45. It will be understood that there remains in the FGD product a substantial amount of unreacted calcium compounds. These unreacted compounds are mixed with fresh milk of lime slurry fed through line 39 into repulper 45 in which a stirring element 41 is provided. There is thus a high utilization achieved of the lime addition to the process. From repulper 45 the milk of lime slurry passes through line 44 to pump 46 which pumps the slurry through line 19 to the injection nozzle or nozzles 23 at spray drying tower 20.
  • FIG. 1 shows a separate repulper 35 in which the milk of lime slurry is prepared, with burnt lime (CaO) for example, introduced through line 37 while water is introduced through line 38.
  • a stirrer 36 is provided for repulper 35.
  • the milk of lime slurry thus prepared in repulper 35 is passed into repulper 45 through line 39.
  • a washing step may be provided. It may be located in line 43 with the FGD product enroute to repulper 45 being washed in water.
  • the chlorides are highly soluble in water and, accordingly, can be drastically reduced or eliminated from the final product by washing.
  • This washing procedure can be carried out with counter current flows in a set of hydrocyclones, thickeners and filters (specific washing circuit not illustrated).

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US06/600,710 1984-04-16 1984-04-16 Method for oxidation of flue gas desulfurization absorbent and the product produced thereby Expired - Fee Related US4544542A (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
US06/600,710 US4544542A (en) 1984-04-16 1984-04-16 Method for oxidation of flue gas desulfurization absorbent and the product produced thereby
CA000473534A CA1224010A (en) 1984-04-16 1985-02-04 Method for oxidation of flue gas desulfurization absorbent and the product produced thereby
ZA85979A ZA85979B (en) 1984-04-16 1985-02-08 Method for oxidation of flue gas desulfurization absorbent and the product produced thereby
DE8585301918T DE3586880T2 (de) 1984-04-16 1985-03-19 Verfahren zur oxydation des absorbents der rauchgasentschwefelung und das dabei hergestellte produkt.
EP85301918A EP0159807B1 (en) 1984-04-16 1985-03-19 Method for oxidation of flue gas desulfurization absorbent and the product produced thereby
ES541606A ES8701518A1 (es) 1984-04-16 1985-03-27 Un metodo para tratamiento de un material de sulfito calcicode granulado fino, en particulas, que es el absorbente ago- tado de un procedimiento de desulfuracion de gas de combus- tion
AT0102685A AT393801B (de) 1984-04-16 1985-04-04 Verfahren zur behandlung von absorptionsmitteln der rauchgasentschwefelung
DK157985A DK157985A (da) 1984-04-16 1985-04-09 Fremgangsmaade til oxidation af et ved afsvovling af roeggas brugt absorberingsmiddel og det ved fremgangsmaaden vundne produkt
JP60081213A JPS60232233A (ja) 1984-04-16 1985-04-16 煙道ガス脱硫吸收剤の酸化方法、及びこれによつて得た生成物
AU41293/85A AU4129385A (en) 1984-04-16 1985-04-16 Calcium sulphate from oxidation of flue gas desulfurization process
CN198585104649A CN85104649A (zh) 1984-04-16 1985-06-15 烟道气脱硫吸收剂的氧化方法及其生产的产品
ES555055A ES8707288A1 (es) 1984-04-16 1986-05-16 Un procedimiento de desulfuracion de gas de combustion seco

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US4666694A (en) * 1984-04-12 1987-05-19 A/S Niro Atomizer Method for treating by-products from flue gas
US4917024A (en) * 1989-05-24 1990-04-17 Florida Institute Of Phosphate Research Coal fired power plant with pollution control and useful byproducts
US4985081A (en) * 1989-03-17 1991-01-15 Oy Iampella Ab Method of producing cement or concrete
WO1993002774A1 (en) * 1991-08-01 1993-02-18 Niro A/S Process of producing calcium hydroxide for fluidized bed absorption
DE4231548A1 (de) * 1991-09-27 1993-04-08 Air Prod & Chem Verfahren zur herstellung von flocken aus gipscalciumsulfatdihydraten
US5324501A (en) * 1989-04-26 1994-06-28 A.I.R. Lippewerk Recycling Gmbh Method for the preparation of low-chloride plaster products from calcium-containing residues of flue-gas purification plants
US5516976A (en) * 1994-08-26 1996-05-14 Southwind Enterprises Inc. Sulphate agglomeration
US5722929A (en) * 1994-08-26 1998-03-03 Southwind Enterprises Inc. Particle agglomeration with acidic sulphate
US20020021994A1 (en) * 1999-10-08 2002-02-21 Blue Jerry D. Sulfur recovery gasification process for spent liquor at high temperature and high pressure
US6471767B1 (en) 1999-10-15 2002-10-29 American International Materials, Ltd. Process for recycling gypsum-based waste material into readily crushable members for use in the manufacture of cement and crushable members formed thereby
US20060093540A1 (en) * 2003-02-06 2006-05-04 The Ohio State University Separation of carbon dioxide (CO2) from gas mixtures by calcium based reaction separation (CaRS-CO2) process
US20060211571A1 (en) * 2005-03-17 2006-09-21 Iyer Mahesh V High temperature CO2 capture using engineered eggshells: a route to carbon management
US20080105121A1 (en) * 2006-11-03 2008-05-08 Ramsay Chang Sorbent filter for the removal of vapor phase contaminants
US20080105120A1 (en) * 2006-11-03 2008-05-08 Mark Simpson Berry Method and apparatus for the enhanced removal of aerosols from a gas stream
US20090263316A1 (en) * 2006-09-25 2009-10-22 The Ohio State University High purity, high pressure hydrogen production with in-situ co2 and sulfur capture in a single stage reactor
CN101430345B (zh) * 2007-11-23 2011-09-14 贵州电力调度通信局 火电厂脱硫上网电量的计算方法
US20120160340A1 (en) * 2010-12-22 2012-06-28 Alstom Technology Ltd Slurry control system
WO2015060795A1 (en) * 2013-10-21 2015-04-30 Dora Teknolojik Bilgisayar Ürünleri Endüstrisi Anonim Şirketi Process for the minimization/elimination of so2 and co2 emission emerging from the combustion of coal
CN108380016A (zh) * 2018-05-09 2018-08-10 福建龙净脱硫脱硝工程有限公司 一种焙烧烟气脱硫脱沥青烟脱氟除尘净化的***及方法
CN108744940A (zh) * 2018-04-24 2018-11-06 北京北科环境工程有限公司 一种脱硫副产物氧化装置
CN111690416A (zh) * 2020-06-24 2020-09-22 青岛智邦炉窑设计研究有限公司 一种利用工业固体废物生产新型土壤调节功能性材料的方法

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DK165674C (da) * 1989-07-17 1993-05-24 Niro Atomizer As Fremgangsmaade til afsvovling af varm roeggas med et i forhold til svovldioxidindholdet lille indhold af hydrogenchlorid
FR2698287B1 (fr) * 1992-11-24 1995-01-20 Stein Industrie Procédé de réduction des émissions de polluants dans les installations de combustion à lit fluidisé circulant.
GB9814508D0 (en) 1998-07-03 1998-09-02 Polycell Prod Ltd Filler material
CN1304088C (zh) * 2005-06-15 2007-03-14 东南大学 基于硫酸钙的煤的置换燃烧法分离二氧化碳的装置及分离方法

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US3480387A (en) * 1966-11-15 1969-11-25 Central Glass Co Ltd Method for producing gypsum pellets
US3563701A (en) * 1967-02-28 1971-02-16 Climax Chem Method of producing sulfate granules and volatile acid gases
US4081513A (en) * 1974-12-11 1978-03-28 The United States of America as represented by Administrator U.S. Environmental Protection Agency Disposal of sulfur oxide pollutant-containing gas
US4053375A (en) * 1976-07-16 1977-10-11 Dorr-Oliver Incorporated Process for recovery of alumina-cryolite waste in aluminum production
US4162170A (en) * 1977-06-29 1979-07-24 Vish Chimiko-Technologicheski Institute Method of obtaining granulated and defluorated phosphogypsum
US4177158A (en) * 1978-02-13 1979-12-04 Chevron Research Company Method for producing an attrition-resistant adsorbent for sulfur dioxide, the resulting composition and a process using same
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Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4666694A (en) * 1984-04-12 1987-05-19 A/S Niro Atomizer Method for treating by-products from flue gas
US4985081A (en) * 1989-03-17 1991-01-15 Oy Iampella Ab Method of producing cement or concrete
US5324501A (en) * 1989-04-26 1994-06-28 A.I.R. Lippewerk Recycling Gmbh Method for the preparation of low-chloride plaster products from calcium-containing residues of flue-gas purification plants
US4917024A (en) * 1989-05-24 1990-04-17 Florida Institute Of Phosphate Research Coal fired power plant with pollution control and useful byproducts
WO1993002774A1 (en) * 1991-08-01 1993-02-18 Niro A/S Process of producing calcium hydroxide for fluidized bed absorption
DE4231548A1 (de) * 1991-09-27 1993-04-08 Air Prod & Chem Verfahren zur herstellung von flocken aus gipscalciumsulfatdihydraten
US5362471A (en) * 1991-09-27 1994-11-08 Air Products And Chemicals, Inc. Process for producing gypsum flake from flue gas desulfurization
US5516976A (en) * 1994-08-26 1996-05-14 Southwind Enterprises Inc. Sulphate agglomeration
US5722929A (en) * 1994-08-26 1998-03-03 Southwind Enterprises Inc. Particle agglomeration with acidic sulphate
US20020021994A1 (en) * 1999-10-08 2002-02-21 Blue Jerry D. Sulfur recovery gasification process for spent liquor at high temperature and high pressure
US6471767B1 (en) 1999-10-15 2002-10-29 American International Materials, Ltd. Process for recycling gypsum-based waste material into readily crushable members for use in the manufacture of cement and crushable members formed thereby
US20080233029A1 (en) * 2003-02-06 2008-09-25 The Ohio State University Separation of Carbon Dioxide (Co2) From Gas Mixtures By Calcium Based Reaction Separation (Cars-Co2) Process
US8226917B2 (en) 2003-02-06 2012-07-24 The Ohio State University Separation of carbon dioxide from gas mixtures by calcium based reaction separation
US7618606B2 (en) 2003-02-06 2009-11-17 The Ohio State University Separation of carbon dioxide (CO2) from gas mixtures
US20060093540A1 (en) * 2003-02-06 2006-05-04 The Ohio State University Separation of carbon dioxide (CO2) from gas mixtures by calcium based reaction separation (CaRS-CO2) process
US20060211571A1 (en) * 2005-03-17 2006-09-21 Iyer Mahesh V High temperature CO2 capture using engineered eggshells: a route to carbon management
US7678351B2 (en) 2005-03-17 2010-03-16 The Ohio State University High temperature CO2 capture using engineered eggshells: a route to carbon management
US20090263316A1 (en) * 2006-09-25 2009-10-22 The Ohio State University High purity, high pressure hydrogen production with in-situ co2 and sulfur capture in a single stage reactor
US7837975B2 (en) 2006-09-25 2010-11-23 The Ohio State University High purity, high pressure hydrogen production with in-situ CO2 and sulfur capture in a single stage reactor
US20100202945A1 (en) * 2006-11-03 2010-08-12 Electric Power Research Institute, Inc. Method and Apparatus for the Enhanced Removal of Aerosols and Vapor Phase Contaminants from a Gas Stream
US8241398B2 (en) * 2006-11-03 2012-08-14 Electric Power Research Institute, Inc. Method and apparatus for the enhanced removal of aerosols and vapor phase contaminants from a gas stream
US20080115704A1 (en) * 2006-11-03 2008-05-22 Mark Simpson Berry Method and Apparatus for the Enhanced Removal of Aerosols and Vapor Phase Contaminants from a Gas Stream
US7708803B2 (en) 2006-11-03 2010-05-04 Electric Power Research Institute, Inc. Method and apparatus for the enhanced removal of aerosols from a gas stream
US7731781B2 (en) 2006-11-03 2010-06-08 Electric Power Research Institute, Inc. Method and apparatus for the enhanced removal of aerosols and vapor phase contaminants from a gas stream
WO2008058027A2 (en) * 2006-11-03 2008-05-15 Electric Power Research Institute, Inc. Method and apparatus for the enhanced removal of aerosols from a gas stream
US20080105120A1 (en) * 2006-11-03 2008-05-08 Mark Simpson Berry Method and apparatus for the enhanced removal of aerosols from a gas stream
US8029600B2 (en) 2006-11-03 2011-10-04 Electric Power Research Institute, Inc. Sorbent filter for the removal of vapor phase contaminants
WO2008058027A3 (en) * 2006-11-03 2008-07-10 Electric Power Res Inst Method and apparatus for the enhanced removal of aerosols from a gas stream
US20080105121A1 (en) * 2006-11-03 2008-05-08 Ramsay Chang Sorbent filter for the removal of vapor phase contaminants
CN101430345B (zh) * 2007-11-23 2011-09-14 贵州电力调度通信局 火电厂脱硫上网电量的计算方法
US20120160340A1 (en) * 2010-12-22 2012-06-28 Alstom Technology Ltd Slurry control system
US9429274B2 (en) * 2010-12-22 2016-08-30 Alstom Technology Ltd Slurry control system
US10343109B2 (en) 2010-12-22 2019-07-09 General Electric Company Slurry control system
WO2015060795A1 (en) * 2013-10-21 2015-04-30 Dora Teknolojik Bilgisayar Ürünleri Endüstrisi Anonim Şirketi Process for the minimization/elimination of so2 and co2 emission emerging from the combustion of coal
CN108744940A (zh) * 2018-04-24 2018-11-06 北京北科环境工程有限公司 一种脱硫副产物氧化装置
CN108744940B (zh) * 2018-04-24 2023-10-20 北京北科环境工程有限公司 一种脱硫副产物氧化装置
CN108380016A (zh) * 2018-05-09 2018-08-10 福建龙净脱硫脱硝工程有限公司 一种焙烧烟气脱硫脱沥青烟脱氟除尘净化的***及方法
CN111690416A (zh) * 2020-06-24 2020-09-22 青岛智邦炉窑设计研究有限公司 一种利用工业固体废物生产新型土壤调节功能性材料的方法
CN111690416B (zh) * 2020-06-24 2021-11-23 青岛智邦炉窑设计研究有限公司 一种利用工业固体废物生产新型土壤调节功能性材料的方法

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EP0159807B1 (en) 1992-12-09
DK157985A (da) 1985-10-17
ES541606A0 (es) 1986-12-01
EP0159807A2 (en) 1985-10-30
DK157985D0 (da) 1985-04-09
CA1224010A (en) 1987-07-14
AU4129385A (en) 1985-10-24
DE3586880D1 (de) 1993-01-21
JPS60232233A (ja) 1985-11-18
ES8701518A1 (es) 1986-12-01
EP0159807A3 (en) 1987-08-26
ATA102685A (de) 1991-06-15
CN85104649A (zh) 1986-12-24
ZA85979B (en) 1985-10-30
DE3586880T2 (de) 1993-04-15
ES555055A0 (es) 1987-07-16
AT393801B (de) 1991-12-27
ES8707288A1 (es) 1987-07-16

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